Composite Materials

ABSTRACT

A mixed metal oxide material of tantalumand titanium is provided for use in a fuel cell. The material may comprise between 1 and 20 at. % tantalum. The mixed metal oxide may form the core of a core-shell composite material, used as a catalyst support, in which a catalyst such as platinum forms the shell. The catalyst may be applied as a single monolayer, and is preferably between 6.5 and 9.3 monolayers thick.

COMPOSITE MATERIALS

The present invention relates to materials for use in a fuel cell and particularly to core-shell composite materials for use in a fuel cell.

A fuel cell comprises an anode for oxidation of a fuel and a cathode where an oxidising agent, such as oxygen, is reduced. Ions are transported between the two electrodes by means of an electrolyte. Fuel supplied to the cell is oxidised at the anode, releasing electrons, which pass through an external circuit to the cathode, where they are consumed during reduction of the oxidising species. In a polymer electrolyte membrane fuel cell (PEMFC), the fuel is usually hydrogen and the oxidising species is usually oxygen. A polymer electrolyte allows protons to flow from the anode to the cathode.

Platinum-containing catalysts are one of the most efficient catalysts for facilitating the oxygen reduction reaction (ORR) at the cathode of a fuel cell. Platinum, however, is a costly material and so methods for reducing the quantity of platinum required for an effective fuel cell are highly sought-after. Traditionally, platinum is dispersed over a carbon support to increase the surface area of the platinum, relative to its mass. A maximum in mass activity is produced with a platinum particle size of approximately 3-4 nm [References 1-4]. In this system, if the particle size of platinum is further reduced, oxygen reduction activity is also sharply reduced, limiting the advantages that can be achieved by dispersion. An additional disadvantage with the system is that the carbon support can become oxidised under fuel cell operating conditions. This oxidation leads to degradation of the catalyst, which limits the lifetime of the fuel cell [5].

Metal oxides have previously been investigated for use as fuel cell catalyst supports [6-18]. Metal oxides are less prone to oxidative corrosion than carbon, and can, therefore, be more stable in a fuel cell environment. The use of metal oxides as supports for fuel cell catalysts and methods of synthesising suitable oxides has been described in, for example, US2009/0065738A1, US2006/0263675, U.S. Pat. No. 7,704,918B2, US2007/0037041A1, WO2008/025751 and WO2009/152003 [14-18].

Core-shell catalysts with Pt as the shell material are reported in the literature [17-28]. A core-shell structure is represented schematically in FIG. 1. Many of the systems described in the literature contain a precious metal core, such as Au or Pd [19-22, 24-26, 28]. Consequently, although there is a potential reduction in the quantity of platinum required to produce an effective catalyst, use of another expensive metal within the core, keeps costs high. Other reported core materials include base metals (Cu [27], for example), which are more cost-effective than platinum, but likely to be unstable in a fuel cell. Adzic et al [17, 18] disclose a core-shell type structure with a NaWO₃ core. WO2008/025751 [29] discloses a Pt-coated zirconia and cerium-doped zirconia core-shell system.

The present inventors have investigated the use of metal oxides as supports for fuel cell catalysts and have developed a particularly effective core-shell material.

The present invention is based upon the determination that a mixed oxide of titanium and tantalum can be used as a core supporting material and that a critical thickness of platinum applied as a shell can provide bulk platinum-like oxygen reduction behaviour. The critical thickness is thought to be achieved when platinum particles coalesce to form layers, i.e., as a shell.

In its broadest aspect, the present invention provides a mixed metal oxide material of titanium and tantalum.

Preferably, the mixed metal oxide material comprises between 1 and 20 atomic % titanium (on a metals basis, i.e. excluding oxygen).

More preferably, the mixed metal oxide material comprises between 1.3 and 15.8 atomic % titanium.

Suitably, the mixed metal oxide comprises tantalum oxide doped with titanium.

In another aspect of the present invention, there is provided a catalyst support comprising a mixed metal oxide material as described above.

Suitably, the mixed metal oxide material can be used as a support for platinum particles. To achieve similar oxygen reduction activity to that achieved with use of bulk platinum, the platinum is coalesced to form a film or homogenous layer.

A further aspect of the present invention provides a catalytic medium comprising a mixed metal oxide material as described above and a catalyst applied to a surface of the mixed metal oxide material.

Preferably, the catalyst is applied as a catalytic layer to the mixed metal oxide material.

In a preferred embodiment, the mixed metal oxide material is formed as a core particle.

Preferably, the core particle has a diameter of 10-50 nm, more preferably 10-25 nm.

Preferably, the catalyst is applied as a shell on the core particle.

Alternatively, the mixed metal oxide material is formed as a layer structure.

Suitably, the catalyst comprises platinum or platinum alloy.

Preferably, the catalyst comprises 1-20 ML (monolayers) of platinum or platinum alloy.

In one embodiment, the tantalum oxide is amorphous, the catalyst comprises at least approximately 4.6 ML of platinum or platinum alloy. More preferably, the catalyst comprises at least between approximately 6.5 and approximately 9.3 ML of platinum or platinum alloy.

According to a further aspect of the present invention, there is provided a method of producing a catalytic medium, the method comprising: forming a mixed metal oxide material as described above; and forming a catalytic layer comprising at least one monolayer of catalyst on the mixed metal oxide material.

In one embodiment, the method comprises forming a catalytic layer of 1 to 20 ML platinum or platinum alloy, preferably at least about 4.6 ML.

Preferably, the method comprises forming a catalytic layer of between approximately 6.5 and approximately 9.3 ML of platinum or platinum alloy.

Another aspect of the present invention provides a catalyst for a fuel cell comprising a mixed metal oxide material as described above.

A further aspect of the present invention provides a fuel cell comprising a catalytic medium as described above.

In a yet further aspect of the present invention, there is provided use of a mixed metal oxide material as described above or a catalytic medium as described above in a fuel cell.

The term monolayer (ML) as used herein is used to mean the equivalent amount of catalytic material which would form a uniform layer of 1 atom thickness on a flat surface. It will be appreciated that, in practice, a surface of the mixed metal oxide is unlikely to be perfectly automatically flat. Accordingly, it will be understood that a 1 ML layer of catalyst on the mixed metal oxide substrate will have areas where there are a plurality of catalyst atoms in a layer and areas where there are no atoms of catalyst.

As used herein the term mixed metal oxide indicates an oxide of a mixture of metals; a mixture of metal oxides; or a combination thereof.

FIG. 1 is a schematic cross-section of a core-shell structure and an equivalent layer structure used to model the core shell particle behaviour;

FIG. 2 is a schematic representation of platinum particle growth and nucleation;

FIG. 3 is a schematic view of an electrochemical array substrate;

FIG. 4 is a chart showing the potential at which 1 μA raw current is reached during the oxygen reduction slow cycling experiment for Pt supported on amorphous and anatase titanium oxide (error bars are plus and minus one standard deviation);

FIG. 5 is a chart showing the potential at which 3 μA raw current is reached during the oxygen reduction slow cycling experiment for amorphous and anatase titanium oxide (error bars are plus and minus one standard deviation);

FIG. 6 is a chart showing an example O₂ reduction slow cycling CV for 0.7 ML of Pt supported on amorphous TiO_(x) indicating the two different potentials where ignition potentials have been measured;

FIG. 7 shows four charts illustrating ignition potentials (the potential at which 1 μA raw current is reached) for the oxygen reduction reaction (the second negative going cycle at 20 mV s⁻¹ in O₂ saturated 0.5 M HClO₄) for Pt supported on titanium doped tantalum oxide (atomic percentages of titanium are shown along the bottom of the diagram) before stability cycling;

FIG. 8 shows four charts illustrating ignition potentials (the potential at which 1 μA raw current is reached) for the oxygen reduction reaction (the second negative going cycle at 20 mV s⁻¹ in O₂ saturated 0.5 M HClO₄) for Pt supported on titanium doped tantalum oxide (atomic percentages of titanium are shown along the bottom of the diagram) after stability cycling;

FIG. 9 is images of TaTiO_(x) samples (deposited on silicon wafers) with varying Ti content after exposure to 0.1 M H₂SO₄ for 0, 2, 4, 6 and 24 hours at 80° C.; and

FIG. 10 is a chart comparing of the titanium content (measured by ICP-MS) of titanium doped tantalum oxide samples deposited on silicon wafers before and after 24 hours exposure to 0.1 M H₂SO₄ at 80° C.

For ease of reference, mixed metal oxide materials of titanium and tantalum will be represented as TaTiO_(x). It will be appreciated that this is not a chemical formula indicating any specific stoichiometry, but merely a shorthand indication of the elemental composition of the material. It is not to be taken as limiting the stoichiometry within the mixed metal oxide.

Thin film models of core-shell catalysts for the oxygen reduction reaction in PEM fuel cells have been synthesised with metal oxide cores and a platinum catalyst shell. Metal oxides offer a stable alternative to carbon supports (which are prone to oxidative destruction) and would therefore increase the lifetime of fuel cells.

With reference to FIG. 1, thin film models of core-shell structures have been produced. The structures have a titanium doped tantalum oxide core and platinum shell and have the same (or similar) activity for oxygen reduction as bulk platinum. Traditionally, dopants have been added to metal oxides in order to increase conductivity by creating defects (such as oxygen vacancies). However, in addition to increased conductivity, dopants may also help to create defects on the surface of metal oxides and hence more sites for nucleation of a metal overlayer. The presence of defects cause smaller particles to be formed, leading to a more complete film of metal at a lower equivalent thickness (or loading) (see FIG. 2). A film of platinum potentially has the same oxygen reduction activity as bulk platinum, since a significant number of platinum atoms will be in contact.

Titanium doped tantalum oxide has been investigated as the core supporting material and the equivalent thickness of platinum at which bulk platinum like oxygen reduction behaviour is achieved (the critical thickness d_(crit)) has been identified by the inventors. This appears to be when the platinum particles coalesce to form layers (i.e. a core shell structure) and is evidenced by an overpotential equivalent for the oxygen reduction reaction to that of bulk platinum. On all of the tantalum oxide based supports d_(crit) was found to be between 6.5 and 9.3 ML (monolayers) equivalent thickness of platinum. Performance above this thickness was retained after stability cycling. Investigations described below showed that the support materials are visually stable under warm acidic conditions. It is postulated that, as shown on titanium oxide, mass specific activity on a Pt basis, and stability of the structures could be enhanced by crystallisation of the support (core) materials.

EXAMPLE 1 Synthesis of Samples

Thin film samples were deposited using high-throughput PVD (Physical Vapour Deposition) to model core-shell structures. This system is described in detail elsewhere [30]. A range of oxide samples were synthesised onto different substrates including silicon wafers, quartz wafers and electrochemical arrays (10×10 arrays of gold contact pads as represented in FIG. 3). Titanium and tantalum were deposited from an electron gun (E-gun) source. The TaTiO_(x) films were deposited in the presence of an atomic oxygen source (operating at 600 W power) at a pressure of approximately 5×10⁻⁶ Torr, which would lead to high oxygen stoichiometric materials.

The platinum was deposited onto the pre-deposited oxide thin films from an E-gun source. During deposition the oxide substrates were heated to 200° C. in order to dehydroxylate the surface. A shutter was moved during deposition to allow different equivalent thicknesses of platinum to be deposited onto different fields. These deposition procedures allowed for a varying oxide composition of the support in one direction and a varying amount of platinum in the other orthogonal direction. The amount of platinum deposited was calibrated by depositing thicker films onto silicon substrates and measuring the thickness of the films by AFM (Atomic Force Microscopy). A calibration curve against deposition time was then produced.

EXAMPLE 2 Oxide Characterisation

The composition of the oxide films was determined using a Laser Ablation Inductively Coupled Plasma Mass Spectrometer (LA-ICP-MS, New Wave 213 nm laser & Perkin Elmer Elan 9000). This method gives the relative composition of the metallic elements, but is not capable of measuring the oxygen concentration. As the ICP-MS measurements are destructive, composition measurements were made on samples deposited onto silicon wafers. The same deposition conditions were then used to deposit onto equivalent electrochemical arrays.

X-Ray diffraction (XRD) patterns were obtained using the Bruker D8 Discover diffractometer, a powerful XRD tool with a high-precision, two-circle goniometer with independent stepper motors and optical encoders for the Theta and 2 Theta circles. The D8 diffractometer system was equipped with a GADDS detector operating at 45 kV and 0.65 mA. A high intensity X-ray IμS Incoatec source (with Cu Kα radiation) was incorporated allowing high intensity and collimated X-rays to be localised on thin film materials providing an efficient high throughput structural analysis. This analysis was carried out on oxide films deposited onto Si substrates.

Stability tests were carried out on the oxide films deposited on Si substrates. The samples were immersed in 200 mL of 0.1 M H₂SO₄ at 80° C. for a period of 24 hours. Photographs of the samples were obtained after 0, 2, 4, 6 and 24 hours. ICP-MS was also carried out on the samples before and after this testing.

EXAMPLE 3 Electrochemical Screening

The high-throughput electrochemical screening equipment enables electrochemical experiments on 100 independently addressable electrodes arranged in a 10×10 array in a parallel screening mode which has been described in detail elsewhere [2, 31]. The geometric areas of the individual working electrodes on the electrochemical array are 1.0 mm².

The design of the cell and socket assembly provides a clean electrochemical environment with control of the temperature during experiments. In the experiments described, the temperature was maintained at 25° C. and a mercury/mercury sulphate (MMSE) reference electrode was used. The potential of the MMSE was measured vs. a hydrogen reference electrode prior to screening experiments and all potentials are quoted vs. the reversible hydrogen electrode (RHE). A Pt mesh counter electrode was used, in a glass compartment separated from the working electrode compartment by a glass frit. Various sweep rates were used for different experiments which are outlined in Table 1.

TABLE 1 Electrochemical screening procedure. Sweep Potential limits/ rate/ Experiment Gas V vs. RHE mV s⁻¹ Bubbling Ar 20 min 3 CVs in Ar above solution 0.025-1.200 100 deoxygenated solution O₂ saturation Bubbling Ar 60 s At 1.000 Bubbling O₂ At 1.000 10 min O₂ reduction Bubbling O₂ in Step from 1.00 to 0.60 steps solution and back to 1.00 in 50 mV increments every 90 s 3 CVs in O₂ O₂ above solution 0.025-1.200 5 saturated solution Bubbling Ar 20 min 200 CVs Ar above solution 0.025-1.200 100 stability testing Bubbling with O₂ At 1.000 for 20 min 3 CVs in O₂ O₂ above solution 0.025-1.200 5 saturated solution O₂ reduction Bubbling O₂ in Step from 1.00 to 0.60 steps solution and back to 1.00 in 50 mV increments every 90 s Bubbling CO At 0.075 15 min Bubbling Ar At 0.075 20 min CO stripping Ar above solution 0.025-1.200 100

The electrolyte used for all experiments was 0.5 M HClO₄ prepared from concentrated HClO₄ (double distilled, GFS) and ultrapure water (ELGA, 18 MΩ cm). The gases used (Ar, O₂ and CO) were of the highest commercially available purity (Air Products). Unless stated otherwise, experiments were performed under an atmosphere of argon. Oxygen reduction experiments were performed under an atmosphere of O₂. During potential step measurements, oxygen was bubbled through the electrolyte. Unless noted otherwise, the maximum potential applied to the electrodes was 1.2 V vs. RHE. The screening procedure carried out on each array is outline in Table 1.

EXAMPLE 4 Anatase and Amorphous Un-Doped Titanium Oxide

To compare amorphous and crystalline un-doped titanium oxide (also known as titania) as a support for Pt, separate electrochemical arrays were synthesised. The deposited titanium oxide was amorphous. The titanium oxide was then crystallised by heating in a tube furnace at 450° C. for 6 hours in the presence of oxygen. XRD confirmed that the titanium oxide had been crystallised in the anatase form.

FIG. 4 shows the potential at which 1 μA raw current is reached (threshold values used to measure the onset or ignition potential) during the oxygen reduction slow cycling experiment (i.e. cycling at 20 mV s⁻¹ in oxygenated 0.5 M HClO₄) for various equivalent thicknesses of Pt for Pt supported on amorphous and anatase titanium oxide. An ignition or onset potential is defined as the potential at which the absolute value of the current starts to increase from the background (double layer) level in a cyclic voltammetry experiment, indicating that an oxidation or reduction reaction is taking place. Average results were taken across an array row for identical Pt equivalent thicknesses. This gives a measure of the onset potential of the oxygen reduction reaction. The higher the onset potential, the more active the catalyst for the oxygen reduction reaction. It can be seen that at high equivalent thicknesses of Pt, the ignition potential remains fairly constant with decreasing equivalent thickness of Pt, and similar for both supports.

However, between 5 and 6 ML (monolayers) equivalent thickness of Pt, the ignition potential starts to decrease on both support materials. The effect on the amorphous material is more significant. At 5 to 6 ML for both supports the ignition potential decreases further. On the amorphous titanium oxide at low equivalent thicknesses there is a large amount of scatter in the data. FIG. 5 shows the potential at which 3 μA raw current is reached in the oxygen reduction slow cycling experiment for the same set of data. At this current it is even clearer that the reduction wave is shifted more significantly negative on the amorphous support. This suggests that the anatase support provides better wetting for the platinum and therefore higher activity down to a lower equivalent thickness of Pt.

FIG. 6 shows the voltammetry for one electrode during the oxygen reduction reaction with 0.7 ML equivalent thickness of Pt supported on amorphous titanium oxide. The two currents at which ignition potentials have been measured are indicated with grey lines. Two reduction features are seen: a small feature with a high onset potential, and a larger feature with a low onset potential. These two features are probably due to inhomogeneity within the sample, i.e. some large islands of platinum leading to a high ignition potential and some smaller particles leading to the lower ignition potential. The ignition potential measured at 1 μA raw current gives an indication of the onset of the first reduction feature and the ignition potential measured at 3 μA raw current gives an indication of the onset of the second reduction feature.

These results suggest that the platinum shows slightly better wetting on the anatase titanium oxide, allowing bulk platinum like oxygen reduction activity to a lower equivalent thickness than on amorphous titanium oxide.

EXAMPLE 5 Titanium Doped Tantalum Oxide

TaTiO_(x) films deposited onto silicon wafers at room temperature were confirmed to be amorphous by XRD. Platinum was deposited onto these amorphous supports at 200° C. FIG. 7 shows the potential at which 1 μA raw current is reached (selected to represent the ignition potential) during oxygen reduction slow cycling, before stability cycling, for four different arrays with varying Ti content. Atomic percentages of Ti are shown under each figure. It can be seen that at high equivalent thicknesses of Pt (9.3-23.3 monolayers (ML)), the ignition potentials are high (˜0.9 V vs. RHE) on all of the arrays. This ignition potential is similar to the average ignition potential (at the same current) achieved from an array with a platinum film deposited directly onto the gold contact pads, of 0.915 V vs. RHE.

This suggests that the thickest films deposited onto the tantalum oxide supports approach bulk platinum like behaviour. Below approximately 9.3 ML equivalent thickness, the ignition potentials decrease. This indicates that a higher overpotential is required for equivalent thicknesses below between 6.5 and 9.3 ML. The addition of Ti to the support as a dopant appears to have some effect at keeping the ignition potentials higher than on the pure tantalum oxide support when the Pt equivalent thickness is below 9.3 ML. This suggests that the Ti has some positive effect, possibly by providing additional nucleation sites for Pt particle formation and growth and hence aiding wetting. The amount of Ti dopant does not appear to have a significant effect.

FIG. 8 shows the ignition potentials for the oxygen reduction slow cycling after 200 stability cycles (between 0.025 and 1.2 V vs. RHE at 100 mV s⁻¹ in Ar purged 0.5 M HClO₄). In general, for the electrodes with a low equivalent thickness of Pt (apart from those with little or no Pt, where the ignition potentials were low and stayed low), the ignition potentials generally decreased, i.e. the overpotential for the oxygen reduction reaction increased. On all of the arrays above 14.0 ML equivalent thickness of Pt the ignition potentials remained high and fairly constant, similar to bulk Pt-like behaviour.

There were variable ignition potentials across the arrays at the equivalent thickness of 9.3 ML of Pt suggesting that at this equivalent thickness the film starts to deviate from bulk Pt-like behaviour. There was no obvious trend in Ti content of the support material. The decrease in activity before and after stability cycling does not appear to be due to dissolution of the support material as photos of samples before and after electrochemical screening show very little difference in visual appearance.

The activity for oxygen reduction of these doped tantalum oxide systems could be increased further by crystallisation of the support since anatase titanium oxide has better activity as a support material than amorphous titanium oxide (see FIG. 4 and FIG. 5).

The amorphous TaTiO_(x) materials deposited onto silicon wafers were tested for their stability under acidic conditions by immersing in 0.1 M H₂SO₄ for 24 hours. It can be seen from FIG. 9 that, up to 24.3 at. % titanium doping, the amorphous tantalum oxide appears stable under these conditions.

As indicated above, atomic percentage values given are on the total metal content. That is to say, 46.9 at % Ti indicates 53.1 at % Ta. The exact stoichiometry including oxygen atoms is undefined but is at or close to stoichiometric, thereby maintaining oxide properties.

FIG. 10 shows the titanium content of the doped tantalum oxides before and after acid testing (measured by ICP-MS). It can be seen that titanium is lost from the oxide material under these conditions after 24 hours. This is unsurprising since amorphous titanium oxide is known to be unstable under these conditions. The oxide material does not visually break down which can be attributed to the inherent stability of the tantalum oxide, even whilst amorphous. Stability of the material may be enhanced by crystallisation, which may also lead to better oxygen reduction activity at lower equivalent thicknesses of Pt.

The above experiments show that as the loading of platinum is decreased on all of the support materials studied, the ignition potential for the oxygen reduction reaction initially remains constant. However, below a certain critical thickness (d_(crit)) the ignition potential starts to decrease (i.e. the overpotential for the oxygen reduction reaction starts to increase, or the electrodes are less active for the oxygen reduction reaction). At high loadings of platinum, the ignition potential is similar to a bulk platinum electrode, suggesting a core-shell structure with enough Pt atoms in contact to mimic bulk metal. When the ignition potential starts to decrease, this is because the platinum starts to break into discrete particles.

On the titanium doped tantalum oxide support, the d_(crit) value was between 6.5 and 9.3 ML equivalent thickness of platinum, suggesting that complete films of platinum were achieved within this range. When titanium was added to the tantalum oxide support, there was an enhancement in activity seen below the d_(crit) level, suggesting better wetting of the platinum at reduced loadings.

The loading of platinum needed to achieve bulk platinum like oxygen reduction activity when the platinum is supported on an undoped titanium oxide support was reduced when moving from amorphous to anatase titanium oxide. Therefore, it can be understood that if titanium doped tantalum oxide is crystallised, this may further enhance the oxygen reduction activity. Crystallisation may also enhance the stability of the mixed metal oxide support material.

Use as a Core-Shell Catalyst

The materials described in the present application are readily scaled up from the model thin film samples to bulk core shell powder materials using known techniques. US2010/0197490, US2007/0031722, US2009/0117257, US2006/0263675 and CN101455970 give examples of suitable procedures. Other methods will be readily apparent to the skilled person.

The stability of the materials described in this application is such that the materials are effective for use in fuel cells.

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1-18. (canceled)
 19. A mixed metal oxide material of titanium and tantalum, the mixed metal oxide material comprising between 1 and 20 atomic % titanium, based on metal content.
 20. The mixed metal oxide material as claimed in claim 19, comprising between 1.3 and 15.8 atomic % titanium.
 21. The mixed metal oxide material as claimed in claim 19, wherein the material is formed of tantalum oxide doped with titanium.
 22. A catalyst support comprising a mixed metal oxide material of titanium and tantalum.
 23. A catalyst support comprising the mixed metal oxide material as claimed in claim
 19. 24. A catalytic medium comprising the catalyst support as claimed in claim 22, and a catalyst applied to a surface of the catalyst support.
 25. The catalytic medium as claimed in claim 24, wherein the catalyst support is formed as a core particle.
 26. The catalytic medium as claimed in claim 25, wherein the catalyst is applied as a shell on the core particle.
 27. The catalytic medium as claimed in claim 24, wherein the catalyst support is formed as a layer.
 28. The catalytic medium as claimed in claim 24, wherein the catalyst comprises platinum or platinum alloy.
 29. The catalytic medium as claimed in claim 24, wherein the catalyst comprises at least approximately 1 ML (monolayer) of platinum or platinum alloy.
 30. The catalytic medium as claimed in claim 24, wherein the catalyst comprises at least between approximately 6.5 and approximately 9.3 ML of platinum or platinum alloy.
 31. A method of producing a catalytic medium, the method comprising: forming the catalyst support as claimed in claim 22, and forming a catalytic layer comprising at least one monolayer of catalyst on the catalyst support.
 32. The method as claimed in claim 31, comprising forming a catalytic layer of at least approximately 1 ML of platinum or platinum alloy.
 33. The method as claimed in claim 31, comprising forming a catalytic layer of between approximately 6.5 and approximately 9.3 ML of platinum or platinum alloy.
 34. A catalyst for a fuel cell comprising the catalytic medium as claimed in claim
 24. 35. A fuel cell comprising the catalytic medium as claimed in claim
 24. 36. A fuel cell comprising the mixed metal oxide material as claimed in claim
 19. 37. A fuel cell comprising the catalyst support as claimed in claim
 22. 